Titanocene(III)‐Catalyzed Precision Deuteration of Epoxides

We describe a titanocene(III)-catalyzed deuterosilylation of epoxides that provides β-deuterated anti-Markovnikov alcohols with excellent D-incorporation, in high yield, and often diastereoselectivity after desilylation. The key to the success reaction is novel activation method Cp2TiCl2 (tBuC5H4)2TiCl2 BnMgBr PhSiD3 provide [(RC5H4)2Ti(III)D] without isotope scrambling. It was developed discovering an off-cycle scrambling previously described method. Our precision deuteration can be applied synthesis drug precursors highlights power combining radical chemistry organometallic catalysis.